Lecture #10

Plan:
1. Variational method
2. Rayleigh-Ritz trial functions
3. Derivation of the secular equation
4. H2+ ion full problem and associated challenges
5. Born-Oppenheimer approximation the electronic Hamiltonian
6. Solving the secular equation for the H2+ molecule

Questions you should be able to answer by the end of todays lecture:
1. Understand the idea behind the variational method for approximating
eigenfunctions.
2. Why does bonding occur?
3. How to calculate simple approximations to the molecular orbital in an ionized
Hydrogen molecule.
4. How do the molecular orbitals change as the interatomic distance is decreased
5. What physical insight leads to the separation of the electronic and nuclear
coordinates?
6. How to choose trial wave functions and use the variation principle.


References:

1. Merzbacher chapter 8.
2. Lowe, chapter 7.
3. Dahl Chapter 12 and 13.


The variation method
The problem: in most cases of physical interest the eigenfunctions of the Hamiltonian
cannot be readily found. In such cases one needs to resort to a systematic procedure for
searching for functions which approximate the eigenfunctions. The calculus of variations
provides us with a powerful tool for solving such problems where H is known but not
n
u and
n
E .
The variation method is based on the idea that if we try to find a trial function that
minimizes average E it will be greater or equal than the true ground state eigenfunctions
n
u .
-

-

v
ground state
H d
E H E
d

Proof:
Because H is Hermitian its true eigenfunctions are a complete set therefore any function
and in particular the trial function can be expanded in terms of eigenfunctions:
( ) ( )
1
n
n n
i
x c u x

2
1

n
n n
i
H c E

and
2
1
n
n
i
c

For

ground
E H E it is necessary and sufficient for all 0
n
c except for n=1.
Note: it is possible to find eigenvalues other than the ground energy using the variation
method:

The Rayleigh Ritz trial function
In this method a trial function is chosen as a linear combination of independent and - in
most cases orthogonal and normalized - basis functions . Thus the trial function is of
the form:
1
N
n n
n
c

The trial function can be viewed as a vector in a basis of where the cs are the
components of the vector.

The expectation value is expressed as,

, 1
, 1

N
i i j j
i j
N
i j
i j
c H c
H
H
c c

note: the expression

i j
H is a complex number obtained by performing the integral

i j
H dv

and is called the i,j matrix element of H or

0
i
H
c

and

0
j
H
c

1 , 1 , 1
2
, 1
1 , 1 , 1
, 1
1
, 1

0

N N N
i j j i j i i i j j
j i j i j
N
i
i j
i j
N N N
i j j i j i i i j j
j i j i j
N
i i j j
N
i j
i j j i i i
N
j
i j
i j
H c c c c c H c
H
c
c c
H c c c c c H c
c H c
H c c H c Ec
c c

_

,
_


,

_

,

Yielding n equations with n unknowns since for each ci there is a separate equation, E
being the expectation value corresponding to the optimal choice of the trial function. This
equation is known as the secular equation and we are looking for its roots (i.e the E
values).
( )
1

0
n
i j ij j
j
H E c

in matrix notation,
1 11 12 1
2 21 22
1
....
0
n
n n nn
c H E H H
c H H E
c H H E
1 _
1

1

1
1

, ]
M M


which can only have a non-trivial solution if
( )
1

0
n
i j ij
j
Det H E

_


,

For a case of a set of basis functions which are not orthogonal or normalized, the secular
determinant becomes:

11 11 12 12 1 1
21 21 22 22
1 1
....
0
n n
n n nn nn
H S E H S E H S E
H S E H S E
H S E H S E

M

where the matrix elements are defined in the following way:

ij i j
ij i j
H H dv
S dv

Thus the problem of finding the approximate eigenfunctions and corresponding energy
spectrum has been transformed from one that involves functions and minimization to an
algebraic problem.

The Ritz Theorem: The expectation value of the Hamiltonian is stationary in the vicinity
of its discrete eigenvalues.

All of the intelligence goes into choosing a good trial function, which already contains
in it a large amount of the true eigenfunction. The trial function is chosen with the aid of
physical insight. Hartree Fock method for calculating eigenfunctions of many electron
Hamiltonians is also an example of the variation method.

Understanding the chemical bond - Approximating the wave functions of molecules
LCAO linear combination of atomic orbitals

The problem:

How do we calculate the eigenfunctions of molecules?
The system simple diatomic molecule

I] Draw the potential










R
2
r
1
r
A
B


II] Write the full Hamiltonian
( )
{
2 2 2 2 2 2
2 2 2
1 2
nuclear repulsion
electron-nucleus of electron
energy
attraction

, , , , ,
2 2 2
A B A B r A B
e p p
KE
e e e
H R R r P P p
m m m r r R
_


+ +



,
r r r
h h h
14243 14243



where,

1
2
A
B
r r R
r r R


r
r r
r
r r


In general the wave functions should contain all of the coordinates of the system
Because the protons are 1836 times heavier than the electrons they have much smaller
velocity this means that at the time scales associated with the electronic movement the
protons are stationary.


The Born-Oppenheimer Approximation
Based on the observation that the mass of the proton is approximately 1836 heavier than
the mass of the electron. We assume that due to this mass disparity there is a response
time scale difference between the slow nuclei and the fast electron. We assume that the
motion of the nucleus is adiabatic (i.e. infinitely slow).

(1) The electronic wavefunctions depend only on the positions of the nuclei and not
on their momentum
(2) The positions of the protons are a parameter not a QM variable
(3) Protons have a fixed separation R just add a constant to the energy.
(4) Reduce the three body problem to an electron in a potential
(5) The Hamiltonian is separable


Using the procedure we developed:
Write the Hamiltonian for the electron energy and nuclear repulsion energy.

el
2 2 2 2
2
1 2
H

2
el nr r
e
electronic energy
e e e
H
m r r R

+
r
h
144424443


( ) ( )
2

/
elec elec elec elec
elec nuc nuc rep elec
H u r E u r
E E E e R

+ +

What we have is a functional dependence of the electronic energy on the nuclear
separation ( )
elec
E R .
( ) ( )
{
2 2 2
2 2
nuclear repulsion
energy

,
2 2
A B A B elec
p p
e
H R R E R
m m R
_


+ + +


,
r r
h h

( ) ( ) ( )

, , ,
nuc A B nuc A B nuc nuc A B
H R R u R R E u R R

These eigenfunction reperesent the translation, rotation and vibration states of the crystal.

( ) ( ) ( ) , , ,
Tot A B elec nuc A B
u R R r u r u R R
We would like the find the exact energy eigenfunctions because this is difficult we will
find approximate solutions

el
H u Eu

Assume that our solution can be written as a linear combination of atomic orbitals
( ) ( ) ( )
( )
1 2
0
1 100 1 2 100 2
100 1
1
2
1
r
a
A
B
r c u r c u r
u r e
where
r r R
r r R

r r r
123 14243
r
r
r r
r
r r

The justification for this choice is that when the atoms are infinitely far apart (separated
atom limit) the eigenfunctions should be the exact hydrogen atom functions.
Since this wave function is not an energy eigenfunction we would like to minimize the
average energy or the expectation value with respect to the coefficients,

-
-

v
av
H d
E H
d

( )
( ) ( ) ( ) ( ) ( )
( ) ( )
( )
( ) ( ) ( )
1 2
1 100 1 2 100 2 1 100 1 2 100 2
1 2
1 100 1 2 100 2 1 100 1 2 100 2

,
c u r c u r H c u r c u r dv
E c c
c u r c u r c u r c u r dv

_

+ +

,

+ +

r r r r
123 14243
r r r r

We are now going to apply the variation principle to allow us to find the function
which minimizes E (Cauchy Reiman Theorem).

0
i
E
c

Minimizing the energy expectation value with respect to the coefficients leads us to
the determinant problem,
( ) ( )
( ) ( )
11 11 1 12 12 2
21 21 1 22 22 2
0
0
H ES c H ES c
H ES c H ES c
+
+


11 12 1 11 12 1
21 22 2 21 22 2
11 11 12 12
21 21 22 22
11 12
+
12
11 12
-
12
0
1
E
1 1
1
E
1 1
H H c S S c
E
H H c S S c
H ES H ES
H ES H ES
H H
S
H H
S
1 _ 1 _

1 1
] , ] ,

_ +


+
,
_



,


We get two solutions for the approximate eigenfunctions, where we have used the
normalization condition
( ) ( ) ( ) ( ) ( ) ( ) ( )
12
2 2 2
2 2
1 100 1 2 100 2 1 100 1 2 100 2 1 2 100 1 100 2
1 1
2 2
1 2 1 2
1
2
2 1
S S
dv
c u r c u r dv c u r dv c u r dv c c u r u r dv
c c c c

+ + +
+ +

14243 14243 144424443

which leads to the normalization coefficients for the two approximate eigenfunctions

( )
( )
( ) ( ) ( )
( )
( )
( ) ( ) ( )
100 1 100 2
100 1 100 2
1
2 1
1
2 1
r u r u r
S
r u r u r
S
E E

+
+

<
r r r
r r r

Take a closer look at the integrals,
Get a number of integrals which we will label in the following way:

( ) ( )
( ) ( )
( ) ( )
( ) ( )
( ) ( )
( ) ( )
( )
( ) ( )
( )
100 1 100 1 11
100 2 100 2 22
100 1 100 2 12
100 2 100 1 21
100 1 100 1 11
100
100 2 100 2 22
100 1 100 2 12
100 2 10

1
since is orthonormal
1
i
u r Hu r dr H
u r Hu r dr H
u r Hu r dr H
u r Hu r dr H
u r u r dr S
u r
u r u r S
u r u r dr S
u r u

r r
r r
r r
r r
r r
r
r r
r r
r
( )
( ) ( )
100 100
0 1 21
0 overlap integral are non-orthogonal
i j
u r u r
r dr S

r r
r



The coulomb energy integral:

( ) ( )
( ) ( ) ( ) ( )
1
100 1 100 1 11 22
2 2 2
2
100 1 100 1 100 1 100 1
1 2

2
E coulomb integral
u r Hu r dr H H
e e
u r u r dr u r u r dr
m r r

_ _


, ,

r r
h r r r r
144444424444443 14444244443


The second term in the coulomb integral describes the attractive electrostatic
interaction between the proton B and the electron around proton A tends to lower the
energy.

The resonance energy contribution:
( ) ( )
( ) ( ) ( ) ( )
1
100 1 100 2 12 21
2 2 2
2
100 1 100 2 100 1 100 2
2 1

2
E S resonant integral
u r Hu r dr H H
e e
u r u r dr u r u r dr
m r r

_ _


, ,

r r
h r r r r
144444424444443 14444244443

The interaction leads to the splitting and the creation of two energy levels

The overlap integral tends to destabilize the molecule.

H atom energy
11
H
11 12
H H +
11 12
H H
11 12
12
1
H H
E
S

2
e
E
R

+
2
e
E
R
+
+
11 12
12
1
H H
E
S
+
+

+

E
n
e
r
g
y

(
a
.
u
=

2
7
.
2
1
e
V
)

1
2

1
1.7
Consequences:

1. Odd and even wave functions the odd wavefunction has a node which is located
between the two nucluei.
2. Draw the wavefunction evaluated along the internuclear separation line.



3. Splitting of the energy levels as the internuclear spacing decreases.














4. The total energy of the molecule (including the proton-proton) repulsion.











R
E
e
l

R
E
t

Ro R
E
t

Ro
bonding
anti
bonding


5. The lower electron eigenfunction or state has a corresponding minimum in the
total energy while the higher energy electon state rise monotonically.
6. The internuclear distance at which the system acheives a minimum is the bond
length which is 2
0
R
7. The energy minimum in the lower curve indicates a stable molecule and the
corresponding MO is call bonding MO. The other MO is called antibonding.
8. The electron in the bonding state will have a wavefunction that leads to a high
probability of finding the electron in between the nuclei this allows for the
attractive e-p forces to offset the repulsive p-p interactions.
9. Near the minimum energy,
( )
2
0
2
K
E R R ;
K is the bond stiffness.

10. In diatomic MO we distinguished between and type bonds. What is the
significance of this labeling scheme? Recall that the AO were labeled with s, p, d
labels which were associated with the orbital angular momentum and the
spherically symmetric potential. Since L^2 commuted with the Hamiltonian we
could find a basis set which was common to
2

,
z
L L and the Hamiltonian. In a
linear molecule the rotational symmetry around the z axis is conserved hence
there is a conservation of the

z
L component of the angular momentum that is why
the MO are labeled according to their symmetries.
The angular solutions